Liquid polymeric printing plate compositions comprising a vinyl chloride polymer, a 2-imidazoline and a polyesteramine containing reaction mixture



United States Patent 3,234,156 LIQUID POLYMERIC PRINTING PLATE COMPOSI- TIONS COMPRISING A VINYL CHLORIDE POL- YMER, A Z-IMIDAZOLINE AND A POLYESTER- AMINE CONTAINING REACTION MIXTURE Melvin Niinoy, Hyde Park, Philip K. Isaacs, Brookline, Norman G. Tompkins, Melrose, and Russell L. Haden, Jr., Lincoln, Mass, assignors to W. R. Grace & C0,, Cambridge, Mass, a corporation of Connecticut No Drawing. Filed May 24, 1961, Ser. No. 112,212 11 Claims. (Cl. 260-22) This invention relates to printing plates and more particularly to duplicate plates suitable for use in letterpress printing. In a specific aspect, it relates to thermosett-ing liquid polymeric compositions which are moldable into flexible plastic plates having a degree of hardness suitable .for printing on corrugated boxes and cartons.

The variety of printing operations and the desired reproductive quality require, inter alia, diverse types of printing plates. The selection of a specific type is dependent upon such factors as simplicity or complexity of plate preparation, quality and quantity of printed reproductions, the economics of plate preparation and the specific printing operation. The most desirable plate is one which could be prepared quickly, economically, and give reproductions of a high caliber and at a rapid rate. There is no type of printing plate known which singularly fulfills all printing operations. Each type of plate must be tailored to meet specific printing needs.

The operation ofprinting on cartons or boxes having walls of corrugated fiberboard disposed between smoothsurfaced paperboard requires a special type of plate. The letters and characters on such plates lie in relief and are normally thicker and raised higher than the faces of plates used in other letterpress printing operations. A prime requisite of such plates is that the printing surface must be sufliciently firm to effect a faithful transfer, and yet possess a certain degree of resiliency so as not to crush the corrugated walls of the container when the impression is made.

The box plates nowin use are generally fabricated from sheets of uncured rubber which vulcanize during the molding operation. The use of solid sheets, however, does not always assure fidelity of reproduction because the sheeted material does not readily fill the minute depressions of the mold. Consequently, the printing features of the resulting plate are not as sharp as the original form. In addition, the uncured sheets must be stored under refrigeration to avoid partial curing at room temperature. Such curing introduces molding difiiculties.

It is, therefore, an object of this invention to provide plastic plates which are adaptable for use in printing on corrugated containers. It is another object of this invention to provide liquid, thermosetting polymeric compositions from which cured, flexible letterpress printing plates may be molded.

Briefly stated, this invention comprises compositions of matter which include a halogen-containing polymeric material, a polyesteramine-containing reaction mixture derived by a step-wise reaction of dicarboxylic acids, glycols and amines, and an imidazoline crosslinking agent. The resulting printing plate compositions are thick, flowable liquids, stable at room temperature, which cure rapidly under heat during the press molding operation to form flexible printing plates of excellent quality. Curing is generally effected in about 2 to minutes at about 155 C. to 168 C. The flexibility of the cured plates permits their use on either flatbed or rotary letterpresses. Certain additives, such as moisture-sequestering agents, may be incorporated in the liquid compositions to improve their performance during the molding step and to inhibit formation of bubbles in the plate.

POLYMERIC 'MATERIALS The halogen-containing polymeric materials which are operable in the compositions of this invention include suspension, emulsion, and paste grade homopolymers of vinyl chloride; vinyl chloride copolymerized with another polymerizab-le monomer, such as vinyl acetate, vinylidene chloride, dibutyl maleate, vinyl lauratc, and a host of other polymerizable vinyl esters; and homopolymers and copolymers of vinylidene chloride.

REACTION PRODUCTS CONTAINING POLYES- TERAMINES The polyesteramine-containing reaction mixtures are derived in a two-step process which is comprehensively disclosed in US. patent application Serial No. 112,210, filed May 24, 1961. In the first step, a glycol and a dicarboxylic acid, and preferably in amounts of 0.75 to one mole of the glycol and one mole of the dicarboxylic acid, are contacted under reactive conditions suitable to promote esterification. The water of reaction is continuously removed as it is formed to displace the chemical equilibrium. The first step of the reaction is halted when less than all and preferably when between about 70 percent to percent of the carboxylic groups are consumed. This gives a mixture of products comprised principally of an idealized polyester having a molecular weight of about 5002900, plus a minor amount of various species of products. In the second step, the resulting mixture is then contacted under reactive conditions with an amount of a suitable amine sufficient to react with the residual 30 percent to 10 percent of the carboxylic groups in the mixture. The water is continuously removed and the reaction is taken to completion. This is determined when the flow of distillate ceases. The resulting product is comprised principally of an idealized polyesteramine having a molecular weight of about 600-3000 in admixture with a minor amount'of various species products.

Suitable acids are the saturated straight chain aliphatic dicarboxylic acids containing 3 to 10 carbon atoms, such as malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acids. Appropriate glycols are those containing 2 to 10 carbon atoms, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3- propanediol, 1,6 -hexanediol, and neopentyl glycol.

The reaction is preferably carried out in the presence of a small amount of an esterification catalyst, and generally between about 0.1 percent to- 0.5 percent, based on the weight of the acid, is sufficient. Eifective catalysts include, among others, sulfuric, hydrochloric, and p-toluenesulfonic acids. In addition, an agent may be added to the mixture to chelate and inactivate any metal impurities which may be present in the glycol and acid. These impurities are of such small order that generally between about 0.1 percent to 0.5 percent by weight of the agent, based on the combined weight of the acid and glycol, is sufficient to react with substantially all of such impurities. Suitable agents include the alkali metal polyphosphates, such as sodium and potassium tripolyphosphate.

Esterification is carried out by charging the reactants, catalyst, and the chelating and inactivating agent to an appropriate apparatus and carrying out the reaction under suitable conditions of temperature and pressure. Irrespective of the particular reactive method employed, the water of condensation is continuously removed as formed, and the first step of the reaction is deemed complete solely by the amount of water which is removed from the system. The end point, therefore, is ascertained when between about 70 percent to 90 percent of the carboxylic groups are consumed. Under these conditions, sutlicient 3; V carboxylic groups remainfree for reaction with the subsequently added amine.

While the end point of step one of the reaction is deter}. mined by the consumption .of carboxylic groups, the constitution ofthe resulting reaction mixture is dependent upon the amounts of acid and glycol used in the reaction.

For example, if equimolar= amounts of dicarboxylic acid and glycol are employed, the reaction mixture-will be comprised. of (1) a major'amount of an idealized poly,-

ester having a molecular weight of about 500-1500 and terminated with a hydroxyl group on one end and a car- I boxylic group on the opposite end :of the chain,](2) species of esters having molecular. weights higher and lower than theidealized compound, (3 products diterminated with carboxylic groups, and (4) products 'diterminated with hydroxyl groups.

On the other hand, if an excess.

of acid is used, i.e., of the order of about one; mole of acid for each 0.75 mole-ofglycol, and the reaction isi carried to a point until all of the glycol is consumed, the

resulting mixture will be comprised of (1) a major amount of an idealized polyester having a molecularweight of 5002900 and terminated on each end with carboxylic groups only, and (2) minor amountsof species of esters diterminated with carboxylic groups having molecular weights higher and lower than the idealized compound.

Step two, covering preparation of the final product, is:

derived by contacting the resulting mixture of step one under reactive conditions with an: amount of an amine sufiicient to react with the residual percent to 10 perr.

cent of the carboxylic groups in the mixture. able amines have the formula The oper- I R-NR '-X in which R and R are preferably" lower alkyl groupshav:

ing 1 to 4 carbon atoms, R is preferably a lower alkylene group having '1 to 4 carbonatoms, and X is a memberselected from the group consisting of OH, NH and --NHLR where R is a lower alkyl group. Suitable amines include 3diethylaminopropylaininc, Z-diethyle aminoethylamine, 3-dibutylaminopropylamine, 4-diethylaminobutylamine, .Z-dimethylaminoethylamine, and such alkanol amines as Z-diethylaminoethanol and 2-dimethyl-- aminoethanol.

In carryingout the secondstep of the reaction, the

components are thoroughly stirred during amine addition and throughout the reaction period while a nitrogen atmos phere is maintained to insure against introduction of air into the system. When therequisite amount of amine has been added, the temperautre of the mixture rises about Thereafter, the reaction is carried out under conditions suitable to promoting for-- 20 C. dueto'salt formation.

mation of the polyesteramine';

Whatever reactive conditions and apparatus are used,"

the terminal point of the reaction is determined when substantially all of the residual carboxylic groups in'themix- I ture are consumed. This is ascertained when'the flow of distillate ceases. having a clear-light amber color comprised of-a mixture of constituents. The constitution of this mixture is dependent upon the molar amounts of acid and glycol used The resulting productis a viscous fluid.

Weights than the idealized products terminated on each'end with hydroxyl groups.

compound.

The preparation of ,polyesteramine-containing reaction mixtures is illustrated in ExampleszI, Hand IlI:

Example I A reaction mixture was prepared in an apparatus comprising a pot equipped with mechanical stirreii'thermometer, nitrogen inlet, and a 3-foot unpacked fractionatin'g column maintained at Cfand leading to a condenser r In the first step,- 2,387 'grar'ns;(22.5 moles) of diethylene glycol were charged to therpo't'and thenand receiver.

4,23'4 grams(22.5 moles) of azelaic acid were added with stirring: vAfter all of the acidwas added, 4.23 grams of p-toluenesulfonic acid vwere charged as catalyst, followed by the addition of 6.62 grams of sodium tripolyphosphate.

The mixture wasrdeaerated by stirring. forrlS minutes at a pressure of 20 mm.,Hg under. a nitrogen blanket, and.

then the system was returned to one atmosphere. Both stirring. and the :nitrogen stream .were'maintained'through out the reactionperiod; The reaction .was carried out under: a

tion. lute criterion for obtaining the. desiredproduct, butis illustrative only of one means, by which the product'may be. derived. Since the reaction of 'step one :is purposely an incomplete one, the end point,:is determined solely by the consumption !v of carboxylic groups." Therefore', the

schedule may be modifiedwith variations in the apparatus; The followingschedule wastused in'this particular ex-.. ample.

distill the requisite .amount'of water}: s

Time, minutes Te'inp.,, C. PressuErIe, mm.

During the course of the reaction, the water was continuously removed, and the reaction was stopped when 700 ml; were collected; The total amount oiwater which was removed over the 5 /3-hour ;period.,corresponded to about 86 percent consumption of the available carboxy'lic groups. The'reaction gave .-a mixture of products com-,

prising (1) as' thepredominant constituent, a polyester.

having a moleCulanweight of about -1000 an'd the following idealized structure:

in step one. For example, if equimolar amounts of acid and glycol arecmployedgthen the product of step two will be comprised of (1) a predominant amountof an idealized polyesteramine having a molecular weight of about 600-1600 and terminated on one end with a tertiary amino group and on the other with a hydroxyl group, (2):

polyesterarnines having higher and 7 lower molecular (Structure I) (2) species of esters having" molecular weights'hi'gher.

and lower than the idealized polyester, (3) products diter minated with carboxylic groups; and '(4) products diterminated with hydroxylngroups.

. 726, grams (5.5 8 moles) of B-diethylaminbpropylamine.

were stirred into the foregoing reaction mixtureat T001114 temperature and .while avloidiriggtherintroduction of fair.

compound, (3) fproductstera minated on each end with tertiary amino groups, and (4) a A time-temperature pressure schedule conducive topromoting'rapid ester-ifica This, particular schedu1e,ihowever,is not-an abso-,

Inyother: apparatus, however, more .or less time may be required nea'rthexend of the reaction in order to.

The exothermic nature of the reaction caused the temcollected at the 6-hour period and the reaction was. perature to rise from 22 C. to 45 C. After all of the stopped. This corresponded to substantially complete amine was added, the components were reacted accordconsumption of the residual carboxylic groups. The final ing to the following schedule. The temperature at the product was a viscous fluid of light amber color and was top of the fractionating column was checked frequently 5 comprised of the mixtures as described in Example I.

to be certain that no amine (B.P., 170 C.) was distilling. When equimolar amounts of dicarboxylic acid and Time, mlnutts "Iemp.,C. Pressure, mm. point where '70 percent to 90 percent of the carboxyl Hg groups are consumed, the result is a reaction mixture 1Q comprising products having as the predominant compoggggg nent a product bearing a hydroxyl and a carboxylic group 200-210 700 on opposed ends of the molecular chain. This is illus- 31g gggfgg trated byStructure 1, ab ve. when the mixture is eon- 210 450- 30 tacted with an amount of amine sufficient to react with the residual carboxylic groups, the predominant compo- The water of reaction was continuously removed as the nent resulting thef'eff'dm, bears y y Z l r y reaction progressed, and the reaction was stopped when amino g up QII PP d 5 u t a by Sfffifilre 141 ml. of distillate were collected over the 6 /2-hour IL period. In this case, the 31 ml. of distillate in excess of theoretical was glycol. The product was a clear, light amber liquid having a viscosity of about 2,500 centipoi'ses at C., and was constituted of a mixture comprising (1) as the predominant constituent, a polyesteramine of a molecular weight of about 1100 and having the following idealized structure:

If an excess of acid is used, i.e., of the order of about one mole of acid for each 0.75, and preferably 0.875, mole of glycol, and the reaction is carried to a point until all of the glycol is consumed, the resulting mixture will be comprised of a predominant ester product diterminated with carboxylic groups. When these carboxylic groups 25 are further reacted with an amine, the predominant prod- (Structure II) not will hear tertiary amino groups on each end of the Weights than the id li d Structure, (3) speci Qf mdchain. The use'of excess acid to prepare such products ucts ditermined with tertiary amino groups, and (4) species s n t at 1n EXample III.

of products diterminated with hydroxyl groups. The d-ihy- Example HI droxylated products are inert in the' mixture and simply act as plasticizer when the mixture or reaction products is added to a polymeric material, such as polyvinyl chlo- 40 manner and aPPara'tus sfl s p 376 ride. grams (2moles) of 212 01310 acid, 133 grams (1.75 moles) of 1,2-propanediol, 0.376 gram of p-toluenesulfonic acid,

and 0.509 gram of sodium tripolyphosphate were charged to the mixer and stirred. Agitation was continued and a nitrogen atmosphere was maintained throughout the reaction period. After all reactants were charged, the

v mixture was heated according to the following schedule and at atmospheric pressure:

(2) polyesteramines having lower and higher molecular The process of this example was carried out in a Example I I In this example, the reaction conditions were modified slightly to give substantially the same mixture of reaction products of Example I. A mixing vessel was provided and equipped with mechanical stirrer, nitrogen inlet,

glycol are employed and the reaction is carried to a thermometer, and a fractionating column maintained Time (haurs); 0 at 100 C. which led to a condenser and receptacle. 3 25 170 941 grams (5 moles) of a'zelaic acid were mixed in the 2 170-190 vessel with 530 grams (5 moles) of diethylene glycol 2 190:210 in the presence of 0.94 gram of p-toluenesultonic acid as 1 -210 catalyst. The reaction was carried out in a nitrogen 4 I atmosphere and in the absence of vacuum while con- The water of reaction was continuously removed as tinuously stirring the reactants. The mixture was heated formed, and the flow of distillate ceased after 63 ml. initially to 115 C. and the temperature was gradually were collected. The reaction gave a mixture of products increased to 190 C. over a 4-hour period. At this time, comprised of (1) a major amount of a polyester ditermi- 158 ml. of water were collected, corresponding to 88 pernated with carboxylic groups-and assumed to have the folcent consumption of the available carboxylic groups, and lowing idealized structure:

(Sfiruct'ur III) the reaction was stopped. The resulting reaction product and (2) minor amounts of species of esters dit'erniinated was comprised substantially of the mixtures described in with carboxylic groups having molecular weights higher Example I. p and lower than the idealized structure.

161.4 grams (1.24 moles) of 3-diethylaminopropyl 65 grams (0.5 mole) of 3diethylarriinopropylarnine amine were added to the reaction mixture and the com were thenadded and the mixture was heated first for 5 binedmixture was then reacted in the presence of nitrogen hours at 185-200 C. followed by a 2-hour heating period and in the absence of vacuum. It was initially heated to at 200210 C. Atmospheric pressure was maintained 115 C. and the temperature was then I gradually elethroughout the heating cycle and the water of reaction vated at 220 C. over a 6-hour period while continuously was removed as formed. The reaction ceased after 9 m1.

removing the water of reaction. 20 ml. of water were of distillate were collected, giving a mixture of products" 7. comprising (1) a major? amount of polyesteramine di-J. terminated with tertiary amino groups having the .following idealizedstructu're:

8"" i compounds having more than one imidazoline '-ring.'j These maybe prepared by reacting .monoand. polycarr; boxylic acidsor mixtures thereof with a polyaminehav and (2) minor amounts-of species of polyesteramines dit'erminated with tertiary amino groups having molecular weights higher and lower than the idealized structure;

When compounded with the polymeric material, the realction rnixtures endow the resin with a desirable degree of flexibility while improving its physical and chemical properties. Upon curing in the presenceiof an imidazoline, the polyesteramine'becomeschemically grafted .to

Reaction Conditions Product 'Acid Moles Amine Moles P a H ressure emp., ours 1 }Triethy1ene meme..-" a 760- 150 220 4 V g 6 760-15 150-200 4 1 1 do 2 760-15 150-220 4 1 2 l r 1 dO 1 760-15 150-200 4 1 Diethylene'triamine- 1 760-50 150-200 4 1 d0 v 2 760-50 150-200 4 o 3 }Triethy1ene Terrarium", 8 760- 150-220 4 I Empol 1024i 1 r vi Mixtures of polymerized acids comprising about-'75 percent dimerie and zfipercent trimeric acids derived from a mixture of unsaturatedlS-carbon monocarboxyiic fatty acids.

the resin through its tertiary nitrogen; This results in a.

permanently 'plasticized resin where plasticizer and resin. cannot'beextracted by oils andaliphatic solvents.-

' IMIDAZOLINES' Imi'dazolin'es are strong organic bases, highly reactive with many reagents, and many possess strongsurface ac,-

tivity. The imidazolines which .are'useful inthis in-' To improve the flexibility ofthesplates, the-imidazoline esters of lower alkyl alcohols and {unsaturated fatty acids,

and epoxidized triglycerides of vegetable'oil fatty acids, such asepoXidized-soybun oil and epoxidized castor oil;

vention are 2-substituted-2-imidazoline and 1,2.-disub-- stitirted-Z-imidazoline, and preferably those which in.

themselves are non-volatile and chemically stable at ouring temperatures. In addition, they should be suchthat,

and, in this capacity,.they become grafted to the polymer...

Secondly, they enhance partial grafting of the polyester.- amine plasticizer to the polymer;. This action reduces the tendency of the plasticizer to extractability by oils and.

aliphatic solvents after cure.

The imidazolines may be prepared by contacting appropriate amounts of polyamines and mono-and/ or poly.-"' carboxylic'acids' abreactive temperatures and pressures;

The temperature may range between about 150. C. and;

240 'C. and the operable pressure may range between about .1 min. and 760 mm. Suitable polyamines are ethylene pentamirie. those-.containingfrom 1 to 18 carbon atoms, or even more, such as acetic, caproi c, pelargonic, lauric', palmitic,

oleic, and stearic acids; suitable polycarboxylic :acids include those having from 3 to 36 carbon atoms, such as adipic, pimelic, suberic, azalaic, sebacic, and. dimerized fatty acids. In addition,.mixtures of mono; and/or polyii carboxylic acids may be used It. is, of course',.within the scope of this invention to use polyimidazolines, i.e.,

may be pro-reacted with an epoxy plasticizer before his mixed into the composition. The epoxy groups: help to control and even enhance crosslinkingwithout degrada tion; Effective. epoxy compounds; include epoxidized Reaction of ther imidazoline'andflthe epoxy compound proceeds quite readily when carried;out;at.temperatures,

tween about C and C.

A procedure for. preparing a typicaliepoxy-imidazolinei reactionproduct is illustrate'dtinrExample IVE Example 11! betweensabout '100? Clan-d C., and preferably be- 67.7 pounds (.24 molel'of oleicacid and 36' pounds 7 a (.06 mole) of Empol 1024. 'were mixed together: in a lass vacuum vessel and then 36.4 pounds (.18. mole) of; a

sebacic acidwerc added: The acidsfwere heated to about '70 C;,.and then;70i2 pounds...(.48.mole) of triethylamine tetramine were added; 021 pound. of powdered sodium tripolyphosphate was then added to inactivate and c-helate any metal impurities which ;.may have been present in the :acids and amine. The reactants were vigorously agitated and=a nitrogen atmosphere was applied and maintained throughout the reaction period: The mixture was heatedinitially at one'a'tmosphere to about 150 Ca. and the temperature was gradually raiseduntil aval-ue of about 220 C. was reached over a three-hour period: while, the. pressurev was correspondingly-reduced frornf7 60 to 20; 111111.; Hg; Thereactionwas then continued .fortone hour at220f. and 20 mm.fHg. Waterof condensation was a removed throughout the reaction period asform'ed. The amount of'waterremoved.corresponded with. about 85 percent conversion of=the carboxyls to imidazoline groups, leaving a balance of the carboxyls in the. form of amides asconfirmed by-infrared absorption analysis. 'The pro d-,

not was then cooled to 130 C. pounds of Epoxol 74 were heated to 130 C. in an open vessel and then 10 pounds of the foregoing acids-amine reaction product (already at a temperature of 130 C.) were added slowly with stirring. (Epoxol 74 is an epoxidized soybean oil having an oxirane oxygen content ranging between about 7.0-7.5 percent). The mixture was stirred. gently, held at 130 C. for one hour, and then cooled.

While the halogen-containing polymeric material, the polyesteramine-containing reaction mixture, and the imid azoline product constitute the major ingredients of the printing plate composition, it may be modified by the addition of minor amounts of certain functional constituents. Among these is an agent to sequester any stray moisture which may remain in the composition after it is manufactured or which may accidentally reach the composition during storage and use. Such moisture is undesirable because it tends to form bubbles in the molded plate which adversely affect its printing surface. Any material which would form a compound with water at room temperature and which would not decompose at below about 177 C. would be a suitable moisture-sequestering agent provided it could be reduced to a finely divided state so as to obtain good dispersion and its presence would not cause any undesirable side effects. Quicklime, portland cement, and barium oxide have been found satisfactory for this purpose. White Portland cement is preferred since it can be readily dispersed and results in a more homogeneous print plate.

The printing plate compositions may be prepared by charging the requisite amounts of the ingredients to a suitable apparatus and thoroughly mixing the formulation until all ingredients are uniformly dispersed to yield a homogeneous liquid. A preferred order of compounding is to charge the entire amount of polymeric material and moisture-sequestering agent to a vacuum mixer, and then add the imidazoline and the polyesteramine-containing reaction mixture by increments. The incremental additions are continued until the amounts required by the formulation are thoroughly blended with the other components. The high shear which is developed in this procedure constantly pulverizes any lumps that may form and assures iaintenance of uniform viscosity during the mixing operation and in the final product. When all ingredients prescribed by the formulation have been so processed, the resulting composition is ready for use in molding plates directly in liquid form, or the liquid composition may be partially processed by heating for a time sufficient only to form a solid sheet with a minimum amount of cure.

The liquid compositions are stable at room temperature but solidify and chemically crosslink at curing temperatures. Because of the thermosetting properties of these compositions, the plates produced therefrom may be removed immediately from the mold while hot without causing distortion. This expedient may be contrasted with the practice now followed in separating the commercially-available plastic plates from the mold. In the latter practice, a prescribed cooling cycle must be observed before the plate can be separated in order to avoid distortion of the images. Further, the plates derived from compositions of this invention do not undergo distortion due to cold flow in subsequent, handling, storing and mounting operations. A significant advantage is the nonporosity of the plate surface, which means less ink consumption. In addition, the ordinary ink solvents have less effect on the stability of the plates of this invention than on the rubber plates of commerce which are extensively used in printing on boxes and cartons.

Example V illustrates a composition, compounded according to the foregoing description, and which is suitable for preparing a fiexible plate for printing on boxes and cartons. The composition is a thermosettable liquid, stable at room temperature, which when cured gives a "iii plate having a hardness value of about 30-40, Shore A durometer:

Example V Parts by weight Polyvinyl chloride, paste grade 175 Product of Example IV 200 Product of Example II 200 White Portland cement 15 PLATE MOLDING In preparing duplicate printing plates, a type form is first made by any typesetting process in which the lettering and illustrations on the form are set in relief and in mirror reversal of the original. A matrix or mold is then made of the type form by depressing the relief images into a thermosetting material, such as a phenolic impregnated paperboard, at high temperature wherein a cavity is formed bearing incised positive images. The cavity is filled with a molding compound and subjected to pressure between a pair of heated platens to produce the duplicate plate in which the images lie in relief and in mirror reversal. The duplicate plate is used in the printing operation.

In carrying out the plate-making process with a compo- 'sition such as that of Example V, the matrix is first preheated at about 163 C. for about 3 to 5 minutes. Of course, the preheating period may be reduced by operating at a slightly elevated temperature. The matrix is then laid flat with the cavity side upward and the surface of the cavity is sprayed with a film of a non-volatile fluid, such as a fluid containing a silicone oil. This fluid facilitates subsequent release of the plate from the matrix. The liquid composition is then poured into the warm matrix in amount sufiicient .to fill the cavities completely and the filled matrix is then preheated for about 4 minutes at about 163 C. Thereafter, a sheet of non-shrinkable fabric having a thickness of about .1000 inch and upward is placed on top of the matrix to provide a backing for the plate. Suitable fabrics include square weave glass fabric, various nonawoven cotton materials, and a preferred type is a rosin-sized cotton sheeting sold by Wil lia'mson & Co. as #25 Fabric Shrink Controller. The prime criterion in selecting a suitable material is nonshrinkalbility during plate processing.

A small layer of the composition is then disposed on top of the fabric and this unit is preheated for about 2 minutes at about 163 C. to allow the composition toflow readily over the fabric backing. If a small plate is being prepared, then this preheating step may be dispensed with. The amount of composition which is :poured on the fabric is not critical so long as it, together with the fabric and the height of the printed image, is sufiicient to give at least the desired thickness of the plate. Usually, a slight excess is applied to provide a plate which is slightly thicker than required and the excess is subsequenbly removed by grinding the. cured plate. Finally, the unit is inserted between a pair of press platens, which are heated at about C., andthe press is closed. Press heating is carried out for about 5 minutes, the press is then opened and the cured printing plate is removed. It is usually ground or buried to the desired thickness and is then ready for mounting on the press.

The plates are molded in a standard platemaking press which is generally used in preparing matrices and rubber plastic plates. The equipment is essentially comprised of a hydraulic press which is capable of producing platen pressures of about 1000 pounds per square inch and in which the platens can be heated uniformly with steam or electricity to a temperature of at least about 14'5" C. In the molding operation, the pressure of the platens on the assembled matrix is regulated by bearers disposed on opposed sides of the matrix. These bearers consist simply of strips of metal, the thickness of which corresponds to the thickness of the assembled matrix. When the press is closed, the pressure of the platens is exerted principally on thebearers and the amount of pressure which is applied to the assembled matrix is governed by the corresponding thickness of the bearers. Accordingly, deformation of the matrix is avoided by the usev of such bearers.

The compositions of this invention are stable liquids having excellent castability and ability to print faithful reproductions. Because of its flexible character, the same plate is convertible from rotary to flat bed presses Without .distorting the printed image. In addition, the plates are endowed with controlled shrinkage, long life, good solvent resistance, low ink absorption and good ink transfer. And while the invention has been described with specific use of the compositions in preparing a particular type of printing plate, the compositions are amenable to other uses where the firm and resilient characteristics of the cured flexible polymer are desirable.

The proportions of the components may be varied over wide limits. The halogen-containing polymeric matetrial may constitute about 20-60 percent, preferably 30-45 percent; the moisture-sequestering agent may betbetween 1-5 percent, preferably 2-4 percent; the polyesterarnine containing reaction mixture may be present in amounts of 25-50 percent, preferably 30-40 percent; and the imidazoline, when used alone or when prereacted with an epoxy compound, may be present in amounts of -40 percent, preferably -30 percent. All proportions are based on the total weight of the composition.

We claim: a

1. A liquid thermosettaible composition comprising a halogen containing polymer selected from the group consisting of polyvinyl chloride and vinyl chloride copolym: erized with another polymerizable monomer, an imidazoline derived by reacting a polyamine and a carboxylic acid containing 1 to 36 carbon atoms at a temperature.

ranging between 150 C. and 240 CL, and a polyesterarnine-containing reaction mixture, said reaction mixture 3 being derived by (a) condensing 0.75 mole to one -mole of a glycol and one mole ofan aliphatic dicarboxylic acid while continuously removing the water of condensation therefrom, halting the reaction when less than all of the carboxylic groups are consumed, then (b) contacting the resulting mixture under reactive conditions with .an almout of an amine sulficient to react completely with the residual carboxylic groups in said mixture While con: tinuously removing the water of reaction therefrom, tsaid amine. having the formula R Raine; 7 wherein R and R are lower alkyl groups, R is a lower alkyleue group, and X is a member selected from the group consisting of OH, --NH and -NHR where:

R is an alkyl group.

ZNA composition according to claim 1 whichds supplemented by the addition of a moisture-sequestering agent which is not decomposable at temperatures below.

about 177 C.

3. A composition according to claim 1 wherein the, imidazoline is first prereacted with an epoxy compound before it is incorporated into the composition, said epoxy compound being selected from the group consisting of epoxidized esters of lower alkyl alcohols and unsaturated [fatty acids and epoxidized triglycerides of vegetableoil fatty acids.

4.- A .method for preparing flexible printing plates which comprises pouring the composition of claiml into a cavernous, imageabearing mold in amount sufficient to at least fill the cavity thereof, preheatingthe filled mold,-

and heat-pressing the preheated mold for a period of time azoline derive'd by reacting a polyamine and a 'carboxylic acid containing ,1 to 36 carbon atoms at .a temperature ranging betwen:150 C.i and 240, 0., and a polyester;- amine-containing reaction mixture,'said reaction mixture being derived by (a) contacting under-reactive conditions 0.75 to one mole of a glycolcontainingZ to 10 carbonv atoms and one molei-of an aliphatic dicarboxylicacid con-- taining 3 to. 10 carbon atoms and=halting the reaction when between about percent to percent of the carboxylic groups =areconsumed, then (b) contacting the resulting mixture :under reactive conditions with? an amount of an amine sufiicien-t to react substantially completely with the residualcarboxylic groups: while ;con-

tinuously removing the Water of reaction therefrom, saidgen-containing polymer selected from the group consista ingotf polyvinyl chlorideand vin'yl chloride copolymerized'with another polymerizable monomer, 20-30 percent of an imidazoline derivedtby reacting a polyamine and a carboxylic acid containing 1 to 36 carbon atoms ata tern-1 perature ranging between C. and 240 0., and 30-40 percent of a polyesteramine-containing reaction mixture derived by the reaction described in claiml.

'8. tA- liquid thermosettable composition comprising 30-45 percent of polyvinyl chloride, 20-30 percent of an imidazoline derivedby reacting a polyamine and a carboxylic acidcontaining .1 to 36 carbon atoms at a temperature ranging between 150 C. and-240 C:, and 30-40 percent of a polyesteramine-containing reaction mixture derived by-(a)v contacting equimolaramounts'of aZel-ai-c. acid and diethylene glycol under. reactive condi-I" tions and halting thetreaction when between about 86-88 percent of the carboxylic groups are consumed, and then (b) contacting the resulting mixture under, reactive conditions with anamount of 3- diethylarninopropylamine sufficient to react with the residual .canboxylic groups.

9. A liquid thermosettable composition comprising 30-45 percent of polyvinyl chloride, 20-30 percent of an imidazoline derived ,by reacting. a polyamine and a carboxylic acid containing 1 to 36 carbon atoms at a temperature ranging between 150 C. and 240 C., and 30-40 percent of a polyesteram-ine-containing reactionmixture derived by (a) contacting under reactiveconditions 0.875

mole. .of 1,2-propanediol per mole .od 'azelaic acidand;

halting the: reaction when the ;stoichiometric amount of water is removed, andthe'n (b) contacting the resulting mixture under reactive conditions with 0.25, moleof 3-di-f ethylaminoproplyamine.

' 10.'A'method for preparing ;fle'xible printing plates which comprises pouring the composition of claim 9 intoa cavernous, image-bearing mold-in :amounts sufficient to. at least fill the cavity thereof,ipreheating the filled mold,:

and heat-pressing the: preheated mold :fora period of time suflicient to cure said composition;

11. A liquid thermosettable composition comprising 30 percent polyvinyl chloride, 34 percent of an imid-. azoline-epoxidized soybean reaction product, said imid-f azoline being derived by reacting a polyamine anda can boxylic acid containing :1 to 36 carbonatoms at a ternperature rangingb-etween 150 C; and 240 C., 2 percent.

of Pontlandcement, and 34 percent of apolyesteraminecontaining reaction mixture .derived by (a)v contacting equimolar. amounts of azelaic acid and diethylene glycolunder reactive conditions and halting the reaction when:

between about; 86-88 percent of the carboxylic groups are consumed, and then '(b) contacting the resulting mix ture under reactive conditions. WithHan amount of 3-di-.

13 14 ethylaminopropylamine suflicient to react with the 2,865,927 12/ 1958 Cain 260-309.6 residual carb'oxylic groups. 2,878,233 3/ 1959 Harrison 260-48 2,878,234 3/ 1959 Peterson 260-3096 References Clted by the Examlner 43 4 7 Hageman UNITED STATES PATENTS 5 2,048,778 7/1936 Brwbaker et a1. 260-22 LEON BERCOVITZ Prlmary Exammer- 2,476,832 7/ 1949 Donia 260-896 ALPHONSO D. SULLIVAN, Examiner.

2,555,062 5/1951 Small et a1. 260-75 

1. A LIQUID THERMOSETTABLE COMPOSITION COMPRISING A HALOGEN-CONTAINING POLYMER SELECTED FROM THE GROUP CONSISTING OF POLYVINYL CHLORIDE AND VINYL CHLORIDE COPOLYMERIZED WITH ANOTHER POLYMERIZABLE MONOMER, AND IMIDAZOLINE DERIVED BY REACTING A POLYAMINE AND A CARBOXYLIC ACID CONTAINING 1 TO 36 CARBON ATOMS AT A TEMPERATURE RANGING BETWEEN 150*C. AND 240*C., AND A POLYESTERAMINE-CONTAINING REACTION MIXTURE, SAID REACTION MIXUTRE BEING DERIVED BY (A) CONDENSING 0.75 MOLE TO ONE MOLE OF A GLYCOL AND ONE MOLE OF AN ALIPHATIC DICARBOXYLIC ACID WHILE CONTINUOUSLY REMOVING THE WATER OF CONDENSATION THEREFROM, HALTING THE REACTION WHEN LESS THAN ALL OF THE CARBOXYLIC GROUPS ARE CONSUMED, THEN (BE CONTACTING THE RESULTING MIXTURE UNDER REACTIVE CONDITIONS WITH AN AMOUNT OF AN AMINE SUFFICIENT TO REACT COMPLETELY WITH THE RESIDUAL CARBOXYLIC GROUPS IN SAID MIXTURE WHILE CONTINUOUSLY REMOVING THE WATER OF REACTION THEREFROM, SAID AMINE HAVING THE FORMULA 